Aryl ketone containing organosilicon
materials

ABSTRACT

ORGANOSILICON MATERIALS, INCLUDING MONOMERS AND POLYMERS, AND A METHOD FOR MAKING THEM, ARE PROVIDED. ONE CLASS OF MATERIALS HAVE CHEMICALLY COMBINED *SI-R&#34;-CO-Q UNITS, WHERE R&#34; IS A DIVALENT HYDROCARBON RADICAL AND Q IS A RADICAL SELECTED FROM ARYLLOXYARYL, ARYLTHIOARYL, ARLYSULFONYLARYL, AND CERTAIN HETEROAROMATIC RADICALS. IN ADDITION, ORGANOSILICON POLYMERS AND COPOLYMERS ARE PROVIDED HAVING CHEMICALLY COMBINED *SI-R&#34;-CO-Q UNITS, WHERE Q&#39;&#39; IS A RADICAL SELECTED FROM Q RADICALS, MONOVALENT AROMATIC HYDROCARBON RADICALS AND HALOGENATED MONOVALENT AROMATIC HYDROCARBON RADICALS. THE SUBJECT MONOMERS CAN BE EMPLOYED AS PERFUME OIL BASES IN COSMETICS, ETC. THE SUBJECT POLYMERS CAN BE EMPLOYED AS FLUIDS AND IN THE MANUFACTURE OF ELASTOMERS AND RESINS.

United States Patent 27,281 ARYL KETONE CONTAINING ORGANOSILICONMATERIALS Edward V. Wilkus, Monroe, Conn., and Abe Berger,

Schenectady, N.Y., assignors to General Electric Com- P y No Drawing.Original No. 3,391,109, dated July 2, 1968, Ser. No. 591,118, Nov. 1,1966. Application for reissue June 30, 1970, Ser. No. 51,398

Int. Cl. C081 11/04 US. Cl. 260-465 Y 7 Claims Matter enclosed in heavybrackets II] appears in the original patent but forms no part of thisreissue specification; matter printed in italics indicates the additionsmade by reissue.

ABSTRACT OF THE DISCLOSURE organosilicon materials, including monomersand polymers, and a method for making them, are provided. One class ofmaterials have chemically combined 0 ESiRl'i'lQ units, where R" is adivalent hydrocarbon radical and Q is a radical selected fromaryloxyaryl, arylthioaryl, arylsulfonylaryl, and certain heteroaromaticradicals. In addition, organosilicon polymers and copolymers areprovided having chemically combined I ESiRl JQ units, where Q is aradical selected from Q radicals, monovalent aromatic hydrocarbonradicals and halogenated monovalent aromatic hydrocarbon radicals. Thesubject monomers can be employed as perfume oil bases in cosmetics, etc.The subject polymers can be employed as fluids and in the manufacture ofelastomers and resins.

The present invention relates to organosilicon materials having at leastone aroylorgano radical attached to silicon by carbon-silicon linkages.

The organosilicon materials of the present invention or aryl ketonecontaining organosilicon materials are selected from (A) Silylorganoarylketones of the formula,

O eta 1m Reissued Feb. 15, 1972 and (ii) Copolymers of from 5 to molepercent of (i) units chemically combined with from 95 mole percent to 5mole percent of R SiO units, where R is a member selected frommonovalent hydrocarbon radicals, halogenated monovalent hydrocarbonradicals, cyanoalkyl radicals, halogen radicals, alkoxy, R is selectedfrom R radicals and hydroxy radicals, R" is a divalent hydrocarbonradical selected from arylene radicals and alkylene radicals, Q is amonovalent aromatic radical selected from aryloxyaryl radicals,arylthioaryl radicals, arylsulfonyl aryl radicals, and heteroaromaticradicals having as the hetero atom a member selected from oxygen,sulfur, phosphorous and nitrogen, said heteroaromatic radicals beingselected from five-membered heterocyclic radicals and heterocyclicradicals which are part of a fused ring structure, Q includes all of theaforementioned Q radicals, aromatic hydrocarbon radicals and halogenateda-romatic hydrocarbon radicals, a and b are whole numbers equal to 0 or1, c is a whole number equal to 0 to 3, inclusive, and the sum of b andc in the copolymers of (C) can have a value between 1 to 2.01,inclusive.

Radicals included by R and R of the above formulae are, for example,aryl radicals and halogenated aryl radicals such as phenyl,chlorophenyl, xylyl, tolyl, etc.; aralkyl radicals such as phenylethyl,benzyl, etc.; aliphatic radicals, haloaliphatic radicals andcycloaliphatic radicals such as methyl, ethyl, propyl, butyl, vinyl andallyl, cyclohexyl, trifluoropropyl, trifluorobutyl, cyanoalkyl radicalssuch as cyanoethyl, cyanopropyl, cyanobutyl, etc.; halogen radicals suchas chloro, bromo, etc., alkoxy radicals such as methoxy, ethoxy,propoxy, butoxy, t-butoxy, etc. Radicals included by R of the aboveformulae are arylene radicals, halogenated arylene radicals, alkyleneradicals and halogenated alkylene radicals such as phenylene, tolylene,methylene, ethylene, trimethylene, tetramethylene, pentamethylene,decamethylene, chlorophenylene, etc. Radicals included by Q of the aboveformulae are for example, phenoxyphenyl, furyl, thienyl, xanthenyl,anthryl, xylylsulfonylxylyl, benzofuranyl, carbazolyl, dibenzothienyl,etc. Radicals included by Q are all of the aforementioned Q radicals aswell as monovalent aromatic hydrocarbons and halogenated monovalenthydrocarbons such as phenyl, chlorophenyl, naphthyl, biphenylyl, etc. Inthe above formulae, where R, R, Q and Q respectively can represent morethan one radical, all of these radicals can be the same or a mixture ofany two or more of these radicals.

Some of the aryl ketone containing organosilicon materials of thepresent invention can be made directly by acylating an aryl nucleus,which hereinafter will signify at least one member of a class of arylnuclei which can include hydrocarbons as well as heterocyclics,with asilyl acid halide of the formula,

where R, R" and b are as defined above, and X is a halogen radical, suchas chloro.

Aryl nuclei which can be employed to provide for the aryl ketonecontaining organosilicon materials of the present invention are forexample, benzene, naphthalene, anthracene, diphenylether, furan,thiophene, dixylylsulfone, dibenzofuran, carbazole, dibenzothiophene,etc. Unlike the method shown in our copending application [Sen No.591,117, filed Nov. 1, 1966], Patent 3,410,822, filed concurrentlyherewith and assigned to the same assignee as the present invention,which can provide for the production of dicarbonyl containingorganosilicon materials by deacylating various aryl nuclei, the methodof the present invention provides for production of aryl ketoneconaining organosilicon materials by the monoacylation of heaforementioned aryl nuclei.

Carboxylic acid halides of Formula 5, and methods for naking them, areshown by Sommer et al., J.A.C.S. 73, F130 (1951). Included by thecarboxylic acid halide of *ormula are beta-trichlorosilylpropionylchloride, gamna-methyldichlorosilylbutyryl chloride,gamma-phenylnethylchlorosilylbutyryl chloride, trimethylsilylpropionyl:hloride, etc.

Acylation catalysts that can be utilized to effect reaction wetween thesilyl acid halide of Formula 5, with the aryl nucleus in accordance withthe practice of the invention, nclude for example, aluminum chloride,boron trichloide, zinc chloride, stannic chloride, polyphosphoric acid,IOI'OII trifiuoride, etc.

Organosilicon polymers of the present invention having hemicallycombined siloxy units with aroylorgano radials attached to silicon, asshown by Formula 2, can be nade by either hydrolyzinghalosilylorganoaryl ketones of he formula,

X ,SiR' Q XJ-hSiR"CQ' DI'OdUCCd by acylating various aryl nuclei withcertain of he silyl acid halides of Formula 5, or by cohydrolyzing uchhalosilylorganoaryl ketones with organohalosilanes f the formula,

vhere R, X, b and c are as defined above.

Included by organohalosilanes of Formula 7 are for ex- .mple,methyltrichlorosilane, silicon tetrachloride, methylrhenyldibromosilane,dimethyldichlorosilane, trimethyl hlorosilane,methylvinyldichlorosilane, methylcyanoethyllichlorosilane, etc.

Some of the silylorganoaryl ketones of Formula 1 are or example,trimethylsilylbutyrylthiophene, l,3-'bis(4-phe-.oxybenzoylpropyl)tetramethyldisiloxane, 1,3 bis(furo-'lpropyl)tetramethyldisiloxane, 2 trimethylsilylpropiolylxanthene,furoylpropyldimethylsilanol, p-phenoxybenoylpropylmethyldimethylsilane,thenoyibutyldimethylhlorosilane, 3-diethoxymethylsilylbutyrylcarbazole.These naterials can be used as perfumes, oil bases in cosmetics, to.

The aryl ketone containing organosilicon polymers of be presentinvention can be fluids, viscous gums, or resinlus solids depending uponthe functionality of the respecive chemically combined units. Thepolymers can be comosed of from 2 to 3 thousand chemically combinedunits, vhile preferably they are composed of from 5 to 500 hemicallycombined units. Among the aryl ketone con aining organosilicon polymers,there are preferred polyflBl'S consisting essentially of chemicallycombined units f Formula 4, and copolymers consisting essentially ofhits of Formula 4 and R SiO units. As indicated previusly, theaforementioned polymers and copolymers can Ie silanol chain-stopped, orif desired, chain-stopped with L3SIO0 5 units.

The aryl ketone containing organosilicon polymers of be presentinvention can be compounded with convenional organopolysiloxaneelastomer materials such 'as ilica fillers, for example, fumed silicaetc., heat-age addiives, plasticizers, pigments, etc. A proportion offrom bout 5 to 300 parts of filler which can include reinforcing s wellas non-reinforcing fillers, such as zinc oxide, ditomaceous earth, canbe employed. Cure of the aryl keone containing organosilicon polymerscan be elfected vith conventional room temperature vulcanizing curinggents, such as methyltriacetoxysilane, or curing agents uch asorganosilicates, in combination with a metal soap uch asdibutyltindilaurate, zinc octoate, etc., as taught by lerridge Patent2,845,541, assigned to the same assignee s the present invention. Aperoxide curing catalyst also an be employed such as benzoyl peroxide,dicumyl perxide, etc., in instances where a heat-cure is desired, such 4as where the. aforementioned polymers are terminated with R SiO unitsand contain chemically combined (C H CH SiO units. In addition, cure canbe effected with the employment of a platinum catalyst as taught forexample by Ashby Patent 3,159,601, Lamoreux Patent 3,220,972, bothassigned to the same assignee as the present invention, in combinationwith chemically combined siloxy units having hydrogen attached tosilicon and siloxy units having alkenyl radicals attached to siliconwhich can be chemically combined with units of Formula 2.

Some of the aryl ketone containing organosilicon materials of thepresent invention can be further shown by the formula,

where R, R" and Q are as defined above, f has a value of from 0 to 2.5,inclusive, g has a value of from 0.001 to 1, inclusive, and the sum of fand g has a value equal to 1 to 3, inclusive. Also included by thepresent invention are disiloxanes having the formula,

where R, R" and Q are as defined above.

In the practice of the invention, the aryl nucleus is acylated with asilyl acid halide as shown in Formula 5 and the resultingsilylorganoaryl ketone is recovered. In instances where there arehydrolyzable radicals attached to silicon, the resulting silylorganoarylketone can be hydrolyzed or cohydrolyzed with halosilanes, as shown byFormula 7, to produce a variety of organopolysiloxane polymers andcopolymers.

In most instances the acylation of the aryl nucleus can be accomplishedby standard Friedel-Crafts methods. Experience has shown however, that amodified Friedel- Crafts procedure is preferably employed when utilizinga silyl acid halide having no more than two carbon atoms between thesilicon atoms and the carbonyl group. It has been found that such silylacid halides, for example, a. silyl propionyl halide, often decomposeswhen mixed directly with a Friedel-Crafts catalyst such as an alumiumhalide in the absence of the aryl nucleus. Instead of forming a stablecomplex with the alumium halide, silyl acid halides having no more thantwo carbon atoms between the silicon atoms and the carbonyl group canpartially decompose to carbon monoxide and the corresponding halosilanesand olefin, if the complex is formed in the absence of the aryl nucleuspreviously described. Generally, any standard Friedel-Crafts acylationprocedure can be utilized for acylating the aryl nucleus. In instanceswhere a silyl acid halide such as propionyl halide is used however, itis preferred to add the Friedel-Crafts catalyst in small increments to amixture of the aryl nucleus and the silyl acid halide.

If desired, a suitable organic solvent can be utilized during theacylation of the aryl nucleus to facilitate the acylation reaction.Suitable organic solvents are any organic solvents that aresubstantially inert to the reactants or to the conditions of thereaction and which facilitate the acylation of the aryl nucleus.Suitable organic solvents include for example, methylene chloride,nitrobenzene, carbon disulfide, etc. Temperatures at which the acylationof the aryl nucleus can be effected can vary widely. For example, arange of from -50 C. to C. has been found operable, while a range ofbetween 0 C. to 50 C. is preferred. Any standard Friedel-Crafts catalystcan be utilized to effect the acy1ation of the aryl nucleus with thesilyl acid halide. A preferred Friedel-Crafts catalyst is alumiumchloride. Other Friedel-Crafts catalysts that can be employed however,are for example, B1 ZnCl H PO SnCl etc.

The acylation of the aryl nucleus will be completed when no furtherhydrogen halide, produced during the acylation reaction, is evolved. Theacylated aryl nucleus then can be hydrolyzed by standard procedures. Anacidified mixture of water and ice can be employed for example. Thecrude product can be extracted by use of a suitable organic solvent, andthen purified in accordance with standard procedures such aschromatography, distillation, etc.

Further reaction of the acylated aryl nuclear also can be achieved suchas alkylation, sulfonation, and other standard reactions analogous tochemical reactions common to organic aromatic chemistry. In addition,the monovalent functional groups on the silicon atom of the silylorganoradical can also be replaced with other monovalent radicals to providefor additional chemical reactions with the acylated aryl nucleus. Forexample, a silicon-carbon cleavage reaction can be utilized to formsilanol radicals. Silicon halogen bonds can be alkoxylated to formalkoxy silanes, etc.

In order that those skilled in the art will be better able to practicethe invention, the following examples are given by way of illustrationand not by way of limitation. All parts are by weight.

Example 1 There was added 130 parts of anhydrous stannic chloride to amixture of 90 parts of trimethylsilylbutyryl chloride, 100 partsmethylene chloride, and 84 parts of thiophene under a nitrogenatmosphere. Hydrogen chloride was continually evolved as the mixture wasstirred resulting in the production of a deep colored complex. Themixture was allowed to warm to room temperature and stirred for anadditional 3 hours. It was then heated to reflux for 3 more hours. Themixture was then stirred with a mixture of crushed ice and dilutehydrochloric acid. After the reaction product had been completelyhydrolyzed, the organic layer was separated, dried and fractionated.There was obtained 70 parts of a product boiling at 134l37 C. at 1.5 mm.Based on method of preparation and its infrared spectrum, the productwas trimethylsilylbutyryl-2-triophene having the formula,

( sM (CH2)a iHiS) Example 2 There was added 130 parts of anhydrousstannic chloride to a mixture of 100 parts of chlorodimethylsilylbutyrylchloride, 100 parts methylene chloride, and 84 parts of thiophene underan inert nitrogen atmosphere. During the reaction the mixture was cooledexternally with an ice bath. A red complex formed and hydrogen chloridewas continuously evolved. The mixture was allowed to warm to roomtemperature, stirred for an additional three hours, and then refluxedfor three more hours. The mixture was poured into a mixture of crushedice and dilute hydrochloric acid, as described above. The organic layerwas dried and fractionated. A 73% yield of product was obtained whichdistilled at 228 C. at 1 mm. Based on its method of preparation and itsinfrared spectrum, the product was 1,3-bis(gamma-thenoylpropyl)tetramethyldisiloxane having the formula,

Example 3 The procedure of Example 2 was repeated, except that prior tothe hydrolysis of the acylated thiophene, there was added to the mixture645 parts of dimethyldichlorosilane. After thoroughly stirring theresulting mixture, it was poured into a mixture of 500 parts of ice and5% solution of hydrochloric acid. The organic layer was separated, andwashed repeatedly with aqueous sodium bicarbonate solution until neutralto litmus; it was dried with anhydrous magnesium sulfate. Based on itsmethod of preparation and its infrared spectrum, the product was apolydimethylsiloxane having terminal a-thenoylpropyldimethylsilyllinkages of the average formula,

Example 4 There was added uniformly over a 30 minute period, 4.2 partsof anhydrous aluminum chloride to a mixture of 15 parts ofdiphenylether, 5 parts of beta-trimethylsilyl propionyl chloride, and 50parts of methylene chloride while the mixture was stirred. During theaddition hydrogen chloride was continuously evolved. The mixture wasthen stirred for an additional hour and then refluxed for two morehours. The mixture was then hydrolyzed in accordance with the proceduredescribed in Example 1, and the crude oily product was purified bychromatography on a column packed with Alcoa F-2O alumina in hexane.Elution with hexane removed the excess diphenyl ether; elution withether gave 7 parts of a colorless oil whose infrared spectrum showedabsorption for alkylaryl ketone at 6.0 microns, for methyl-to-silicon at8.0 microns, and for the trimethylsilyl grouping at 11.6 microns. Inaddition, absorption characterizing diphenyl ether was found at 6.3microns, 6.8 microns, 8.3 microns, 7.5 microns, 13.3 microns and 14.4microns. Based on its method of preparation and its infrared spectrum,the product was (beta-trimethylsilylpropionyl)diphenylether having theformula,

ll 3)3 2)2C 061140 CaH;

Example 5 There was added 3.8 parts of anhydrous aluminum chloride overa period of 30 minutes to a stirred mixture of 5.4 parts ofbeta-dimethylchlorosilylpropionyl chloride, 15 parts of diphenyl ether,and 40 parts of methylene chloride. The mixture was stirred severaladditional hours during which time HCl was continuously evolved. Themixture was then hydrolyzed and the organic product was recovered aspreviously described. A crude oil was obtained which was purified bychromatography on a column packed with Alcoa F-20 alumina in hexane.Elution with hexane removed excess diphenyl ether; elution with diethylether gave 4 parts of a colorless oil. Based on its method ofpreparation and its infrared spectrum which showed absorption foralkylaryl ketone at 6.0 microns, methyl-to-silicon at 8.0 microns, inaddition to linear disiloxane linkages at 9.5 microns, and typicalabsorption for diphenyl ether at 6.35 and 6.8, etc., the product was 1,3bis[beta (phenoxybenzoyl)ethyl]tetramethyldisiloxane having the formula,

The above procedure was repeated except that in place ofbeta-dimethylchlorosilylpropionyl chloride there was employed gammadimethylchlorosilylbutyryl chloride. There was obtained a colorless oilwhich was 1,3-bis[gamma (phenoxybenzoyl) propyl] tetramethyldisiloxanehaving the formula,

Example 6 There was added 3.5 parts of anhydrous aluminum chloride to astirred mixture of 4 parts of xanthene and 4.1 parts ofbeta-trimethylsilylpropionyl chloride in 50 parts of methylene chloride.During and after the addition was completed, HCl was continuouslyevolved. The mixture was stirred for an additional 8 hours. It was thenhydrolyzed and the crude product was recrystallized from a hexenetoluenemixture. A white crystalline solid having a melting point of 94-94.5 C.was obtained. Based on its method of preparation and its infraredspectrum showing absorption at 6.0 microns for carbonyl-to-aryl linkagesas well as absorption for the presence of trimethylsilyl at 11.5 to 12microns, plus absorption characteristics of monosubstituted xanthene,the product was beta-trimethylsilylpropionylxanthene having the formula,

ah w zh 13119 Example 7 The procedure of Example 6 was repeated, exceptthat in place of 4.1 parts of beta-trimethylsilylpropionyl chloridethere was utilized 4.5 parts of gamma-trimethylsilylbutyryl chloride. Acrude product was obtained Which was recrystallized from ahexene-toluene mixture. There was obtained 1.4 parts of a whitecrystalline solid having a melting point of 97 98 C. Based on its methodof preparation and its infrared spectrum the product wasgammatrimethylsilylbutyrylxanthene having the formula,

l? H3) (011.)30 131 0 Example 8 There was added over a 30 minute period,3.9 parts of anhydrous aluminum chloride to a stirred mixture of 15parts of dibenzothiophene and parts of gamma-trimethylsilylbutyrylchloride in methylene chloride. Hydrogen chloride was continuouslyevolved during the addition. The mixture was stirred for an additional 8hours, after which it was refluxed for 1 hour. The mixture was thenhydrolyzed and the crude product was purified by chromatography on acolumn packed with Alcoa F-2O alumina in hexane in accordance with theprocedure described above. Hexane elution removed the excessdibenzothiophene; ether gave a 61% yield of yellow solid. Based on itsmethod of preparation and its infrared spectrum, the product wasgamma-trimethylsilylbutyryldibenzothiophene having the formula,

(CH )3Si (CH2) (C i2H7S) Example 9 There was added 4.2 parts ofanhydrous aluminum chloride to a stirred mixture of parts ofdibenzofuran and 5 parts of beta-trimethylsilylpropionyl chloride in 50parts methylene chloride. After the addition, the mixture was stirredcontinuously for several hours to eflect the separation of hydrogenchloride. A crude product was obtained in accordance with the previouslydescribed procedure by hydroylsis and recovery techniques. It wasrecrystallized from hexane. A 51% yield of solid was obtained; the solidhad a melting point of 65 to 67 C. Based on its method of preparation ofits infrared spectrum the solid wasbeta-trimethylsilylpropionyldibenzofuran having the formula,

0 Ha)a Hz)a n v Example 10 There was added 9 parts of anhydrous aluminumchloride to a mixture consisting of 100 parts anhydrous benzene and 14parts of dichloromethylsilylpropionyl chloride under a nitrogenatmosphere. The addition was performed over a period of two hours atambient temperatures. As the reaction proceeded, a deep red complexdeveloped and copious amounts of HCl gas were evolved. After theaddition the reaction mixture was refluxed for 6 hours. A deep red colorsolution was obtained. The solution was divided equally into twoportions. Fraction 1 was poured onto parts ice and heated on a steambath to effect hydrolysis. Two layers developed. The organic layer wasseparated, washed to neutrality, dried, and solvent stripped. A viscousoil remained behind having a pleasant odor. An infrared scan showedcarbonyl absorption at 5.95, some silanol absorption at 2.95 and a broadsiloxane absorption at 9.l10.4 microns. Based 011 method of preparation,the product was a mixture of linear and cyclic material composed ofchemically com bined CH3 0 S iO eHsfl z Hz units.

There was added 65 parts of dimethylchlorosilane to the second portionand the above procedure was repeated. A viscous liquid was obtainedhaving an infrared scan similar to the above product having carbonyl andphenyl absorption of diminished intensity. Based on method ofpreparation, the product was a silanol-terminated copolymer composed ofchemically combined CH; 8!. 0 (3H,

units and C H; (can) i: OH2CH2S l 0 units.

A mixture of the above copolymer, tetraethyl silicate and stannousoctoate is made in accordance with the teaching of Berridge Patent2,845,541. There is obtained a tack-free elastomer after 8 hours.

Example 11 There was added 29 parts of a boron trifluorideethyl ethercomplex to a mixture of 68 parts furane and 40 partschlorodimethylsilylbutyryl chloride,, cooled on an ice bath andmaintained under an inert atmosphere. A mild exothermic reactionoccured, The reaction mixture darkened as it proceeded to a deep reddishbrown color. After the addition, the mixture was poured onto crushedice. There was added 100 parts of chloroform to effect separation. Theorganic phase was recovered and washed to neutrality with sodiumbicarbonate solution, dried and stripped. There was obtained 15 parts ofa liquid product having a pleasant odor. Infrared showed carbonyl absorption at 5.89 microns, absorption at 3.10-3.30 microns showed silanol. Ithad a B.P. of 8587 C. at 1 mm. Based on method of preparation and itsinfrared absorption, the product was 0 HOSRCHaCHz (C4Ha Example 12 Therewas added 13.3 parts of aluminum chloride to a mixture of 22.6 partstrichlorosilylpropionyl chloride and parts benzene maintained under anitrogen atmosphere. The addition was performed at room temperature overa 3 hour period. A red colored complex formed which gradually darkened,the evolution of hydrogen chloride was observed. After the addition, thereaction was brought to reflux and held there for 5 hours. The abovemixture is divided into two portions. There is added to one portion ofthe mixture 15 parts of phosphorous oxychloride. The mixture is stirredand a precipitate of an aluminum chloride-phosphorous oxychloridecomplex results. The mixture is filtered and the organic layer stripped.There is obtained a crude liquid product. Its infrared spectrum isconsistent with the formula,

Hydrolysis of the other portion of the mixture was effected by pouringit onto 30 parts ice; it was then heated on a steam bath. A crudeproduct was recovered with chloroform which was added to the mixture;the organic layer was separated, washed to neutrality, dried andstripped. A 45% yield of resin was obtained which could be drawn intofilaments. An infrared scan of the material showed carbonyl absorptionat 5.98 microns, a very broad siloxane absorption from 8.5 to 10 micronsand a silanol absorption. Based on its method of preparation andinfrared spectra, the product was a polymer which consisted essentiallyof chemically combined oflmdornomsiom units.

The mixture of the above polymer and 10% by weight of the polymer ofmethyltriacetoxysilane is allowed to cure under atmospheric conditions.A tack-free elastomer is obtained after 10 hours.

Although the foregoing examples have been limited to only a few of thevery many variables Within the scope of the present invention, it shouldbe understood that the present invention is directed to a methodinvolving the acylation of a much broader class of aryl nuclei withsilyl acid halide of Formula in the presence of a Friedel- Craftscatalyst. Also, the aryl ketone containing organosilicon materials thatare included within the scope of the present invention are shown byFormula 1, as well as polymers which can have chemically combined unitsof Formula 2.

What we claim as new and desire to secure by Letters Patent of theUnited States is:

1. Aryl ketone containing organosilicon [arganosilicon] materialsselected from the class consisting of,

(A) silylorganoaryl ketones 09 the formula,

0 l 1, ads )RzSz (M) [(A)] (B) polymers consisting essentially ofchemically combined units of the formula,

[(B):| (C) copolymers composed of 0.01 to 99.99 mole percent oforganosiloxy units of the formula,

o'ba'sio Q Me loand 10 (ii) copolymers of from 5 to mole percent of (i)units chemically combined with from 95 mole percent to 5 mole percent ofR SiO- units, where R is a member selected from the class consisting ofmonovalent hydrocarbon radicals, halogenated monovalent hydrocarbonradicals, and cyanoalkyl radicals, R is selected from R radicals andhydroxy radicals, R" is a divalent hydrocarbon radical selected from theclass consisting of arylene radicals and alkylene radicals, Q is amonovalent aromatic radical selected from the class consisting ofaryloxyaryl radicals, arylthioaryl radicals, arylsulfonylaryl radicals,and heteroaromatic radicals having as the hetero atom a member selectedfrom oxygen, sulfur, phosphorus and nitrogen, Q includes all theaforementioned Q radicals, aromatic hydrocarbon radicals and halogenatedaromatic radicals, [Q is a member selected from the class consisting ofaryloxyaryl radicals, arylthioaryl radicals, and arylsulfonylarylradicals, heteroaromatic radicals having as the hetero atom a memberselected from the class consisting of oxygen, sulfur, phosphorus andnitrogen, aromatic hydrocarbon radicals and halogenated aromatichydrocarbon radicals,] a and b are [is a] whole [number] numbers equalto 0 or 1, c is a whole number equal to 0 to 3, inclusive, and the sumof b and c in the copolymers of [(B)] (C) have a value between 1 to[2.0], 2.01, inclusive.

2. Silylorganoaryl ketones in accordance with claim 1 of the formula,

where R is a member selected from the class consisting of monovalenthydrocarbon radicals, halogenated monovalent hydrocarbon radicals, andcyanoalkyl radicals, R is selected from R radicals and hydroxy radicals,[R'] R" is a divalent hydrocarbon radical selected from the classconsisting of arylene radicals and alkylene radicals, Q is a monovalentaromatic radical selected from the class consisting of aryloxyarylradicals, arylthioaryl radicals, arylsulfonylaryl radicals, andheteroaromatic radicals having as the hetero atom a member selected fromoxygen, sulfur, phosphorous and nitrogen, and a is a whole number equalto 0 to 1.

3. Polymers in accordance with claim 1 consisting essentially ofchemically combined units of the formula,

u t n I, [a CRS10 Q CR S10 where R is a member selected from the classconsisting of monovalent hydrocarbon radicals, halogenated monovalenthydrocarbon radicals, and cyanoalkyl radicals, [R] R" is a divalenthydrocarbon radical selected from the class consisting of aryleneradicals and alkylene radicals, Q is a member selected from the classconsisting of aryloxyaryl radicals, arylthioaryl radicals,arylsulfonylaryl radicals, and hetero-aromatic radicals having as thehetero atom a member selected from oxygen, sulfur, phosphorous andnitrogen, aromatic hydrocarbon radicals and halogenated aromatichydrocarbon radicals, and b is a whole number equal to O or I.

4. Copolymers in accordance with claim 1, composed of 0.01 to 99.99 molepercent of organosiloxy units of the formula,

chemically combined with 99.99 mole percent to 0.01 mole percent ofunits of where R is a member selected from the class consisting ofmonovalent hydrocarbon radicals, halogenated monvalent hydrocarbonradicals, and cyanoalkyl radicals, [R'] R" is a divalent hydrocarbonradical selected from the class consisting of arylene radicals andalkylene radicals, Q is a member selected from the class consisting ofaryloxyaryl radicals, arylthioaryl radicals, arylsulfonylaryl radicals,and heteroaromatic radicals having as the hetero atom a member selectedfrom oxygen, sulfur, phosphorus and nitrogen, aromatic hydrocarbonradicals and halogenated aromatic hydrocarbon radicals, b is a wholenumber equal to to 1, c is a whole number equal to 0 to 3, inclusive,and the sum of b and c can have a value between 1 to 2.01, inclusive.

5. Curable compositions in accordance with claim 1 comprising (A) asilanol reactive curing agent in an amount sufficient to effect the roomtemperature vulcanization of said curable compositions, and (B) asilanol chain-stopped polymer consisting essentially of chemicallycombined units of the formula,

O R 0 [Q' HJR'SiO] QPJR'H SiO where R is a member selected from theclass consisting of monovalent hydrocarbon radicals, halogenatedmonovalent hydrocarbon radicals, and cyanoalkyl radicals, [R'] R" is adivalent hydrocarbon radical selected from the class consisting ofarylene radicals and alkylene radicals, and Q is a member selected fromthe class consisting of aryloxyaryl radicals, arylthioaryl radicals,arylsulfonyl aryl radicals and heteroaromatic radicals having as thehetero atom a member selected from oxygen, sulfur, phosphorous andnitrogen, aromatic hydrocarbon radicals and halogenated aromatichydrocarbon radicals.

6. Curable compositions in accordance with claim 1 comprising (A) asilanol reactive curing agent in an amount sufficient to effect the roomtemperature vulcanization of said curable compositions, and (B)copolymers of from 5 to mile percent of units, chemically combined with95 mole percent to 5 mole percent of R SiO units, where R is a memberselected from the class consisting of monovalent hydrocarbon radicals,halogenated monovalent hydrocarbon radicals, and cyanoalkyl radicals,[R'] R is a divalent hydrocarbon radical selected from the classconsisting of arylene radicals and alkylene radicals, and Q is a memberselected from the class consisting of aryloxyaryl radicals, arylthioarylradicals, arylsulfonylaryl radicals, and heteroaromatic radicals havingas the hetero atom a member selected from oxygen, sulfur, phosphorousand nitrogen, aromatic hydrocarbon radicals and halogenated aromatichydrocarbon radicals.

7. A curable composition in accordance with claim 6 where the curingagent is methyltriacetoxysilane.

References Cited The following references, cited by the Examiner, are ofrecord in the patented file of this patent or the original patent.

UNITED STATES PATENTS 2,938,047 5/1960 Black. 2,957,899 10/1960 Black etal. 3,301,817 1/1967 Wilkus et al. 26046.5

DONALD E. CZAJA, Primary Examiner M. I. MARQUIS, Assistant Examiner U.S.Cl. X.R.

252522 R; 260375 B, 46.5 G, 46.5 B, 236.6 R, 448.2 N, 448.8 R

